Electrolysis of pure water in a thin layer cell

Transcription

1 Electrolysis of pure water in a thin layer cell Koichi Jeremiah Aoki*, Chunyan Li, Toyohiko Nishiumi, Jingyuan Chen Department of Applied Physics, University of Fukui, Bunkyo, Fukui, Japan Key words: dissociation kinetics of water; resistivity of water; electrolysis of pure water in thin layer cell; Nernst-Planck equation * Ph one , Fax , kaoki@u-fukui.ac.jp (k.j. Aoki) 1

2 1. Introduction Micro-reactors have been employed for synthesizing small amounts of unstable chemicals for immediate use [1,2]. They are suitable for reactions under conditions of uncommonly high temperature, high concentration and high purity. In addition, they can control such accurate reaction parameters as to achieve subtle mixing and localized concentration [3]. These advantages can be realized in electrochemical micro-reactors, which facilitate ionic transport due to local electric fields, interaction of products at an anode and a cathode, and occurrence of unexpected reactions with salts [4,5]. Several examples can be cited briefly in the following. Micro-electrolysis can be performed at low concentration of supporting electrolyte because of low solution resistance in a small cell [6-9]. The flow cell with a narrow electrode separation has allowed electrochemical treatments of water without supporting electrolytes [ 10 ]. Mass transport of electrochemical products to a counter electrode has been discussed in the light of optimization of cell structures [11]. Electrolysis voltage at segmented electrodes has been controlled locally to a diffusion limited value [12]. Although reaction potential cannot be poorly controlled in conventional, synthetic cells, micro-reactors have made it possible to obtain cyclic voltammograms [13]. Microfluidic channel flow devices have been fabricated for in situ simultaneous hydrodynamic electrochemical ESR, resulting in minimal dielectric loss and a high level of sensitivity [14,15]. Generator-collector experiments in flow cells have been made at a single macroelectrode, and used to detect local ph changes adjacent to the electrode surface [16,17]. Electrochemical coupling between parallel microbands in the linear microchannel is useful for evaluating in situ the average velocity rates of the flow [ 18 ]. Recent work on electrochemical micro-reactors has been reviewed and a number of examples can be seen [19]. Conductivity of solution at low concentration of supporting electrolyte varies with an advance of reactions because reaction products have electric charge different from 2

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5 Voltammetry was made in nitrogen atmosphere covered with a plastic bag under the nitrogen gas pressure slightly larger than the atmospheric pressure at room temperature (24 ± 2 C). The water in the cell was quiescent. Voltammograms for decomposition of water without solution resistance were obtained in 0.1 mol dm^-3 NaClO_4 aqueous solution at film-coated platinum rods. Reproducibility of the voltammograms was confirmed by overlap of three times voltammograms. 3. Results and Discussion 3.1 Computation of concentration profiles At parallel electrodes with a very narrow inter-electrode distance, w, the product H^+ at the anode reacts with the product OH^- at the cathode to reach the equilibrium. Then the redox cycle occurs to enhance the current. Conditions of causing the redox cycle may depend not only on w and k_r but also on fluxes of the ions by diffusion and electric migration. Therefore we formulate here the mass transport. The concentrations of H^+ and OH^-, denoted by c_+ and c_- respectively, are satisfied with the continuum and kinetic equation for fluxes J_+ of H^+ and J_ of OH^- 5

6 where D is the diffusion coefficient common to both ions. Although the diffusion coefficient of H^+ is four times larger than that of OH^-, we use this assumption in order to know approximately potential and concentration distributions in the cell rather than to fit experimental data. Elimination of J± from eq. (2) and (3) yields In contrast, the potential distribution is determined by Poisson's equation: 6

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8 The finite difference form of Eq. (5) is Boundary conditions (6) and (7) converted for Eq. (8) and (9) are given by 8

9 We express the dimensionless current density in terms of the thickness of the reaction layer [41], (D/k_d)^1/2, in order to discuss a relatioship between j and w. Then it is rewritten as

10 3.2 Voltammetry of pure water

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12 4. Conclusions 12

13 value of the diffusion coefficients and to use of the Dirichlet boundary conditions. Therefore they are not suitable for curve fitting to the experimental data. Acknowledgement This work was financially supported by Grants-in-Aid for Scientific Research (Grants ) from the Ministry of Education in Japan and a research fund by Permelec Electrode LTD. 13

14 Figure Captions Figure 2. Illustration of the thin layer cell and two platinum rod electrodes 2.0 mm in diameter used for the experiment. 14

15 Figure 10. Dependence of the resistivity obtained from the slopes in Fig. 9 on w. The dashed line is the resistivity determined by the conductometry. 15

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21 References [1] W. Ehrfeld, V. Hessel, H. Lowe, Microreactors, First edition, Wiley-VCH, Weinheim (2000). [2] C. Wille, R. Pfirmann, Chemistry Today (2004) 20 [3] V. Hessel, H. Lowe, Chem. Ingenieur Tech. 74 (2002) 17. [4] H. Lowe, W. Ehrfeld, Electrochim. Acta 44 (1999) [5] P. Watts, S. J. Haswell, E. Pombo-Villar, Chem. Eng. J. 101 (2004) 23. [6] O. Scialdone, A. Galia, C. Guarisco, S.L. Mantia, Chem. Eng. J (2012) 229. [7] C.A. Paddon, G.J. Pritchard, T. Thiemann, F. Marken, Electrochem. Commun. 4 (2002)

22 [8] A. Attour, S. Rode, A. Ziogas, M. Matlosz, F. Lapicque, J. Appl. Electrochem. 38 (2008) 339. [9] A. Attour, S. Rode, F. Lapicque, A. Ziogas, M. Matlosz, J. Electrochem. Soc. 155 (2008) E201. [10] O. Scialdone, C. Guarisco, A. Galia, G. Filardo, G. Silvestri, C. Amatore, C. Sella, L. Thouin, J. Electroanal. Chem. 638 (2010) 293. [11] C. Belmont, H.H. Girault, Electrochim. Acta, 40 (1995) [12] S. Rode, S. Altmeyer, M. Matlosz, J. Appl. Electrochem. 34 (2004) 671. [13] M. Sakairi, M. Yamada, T. Kikuchi, H. Takahashi, Electrochim. Acta 52 (2007) [14] A.J. Wain, R.G. Compton, R.L. Roux, S. Matthews, K. Yunus, A.C. Fisher, J. Phys. Chem. B 110 (2006) [15] A.J. Wain, R.G. Compton, J. Electroanal. Chem. 587 (2006) 203. [16] M.C. Henstridge, G.G. Wildgoose, R.G. Compton, Langmuir 26 (2010) [17] M.C. Henstridge, G.G. Wildgoose, R.G. Compton, J. Phys. Chem. C 113 (2009) [18] C. Amatore, M. Belotti, Y. Chen, E. Roy, C. Sella, L. Thouin, J. Electroanal. Chem. 573 (2004)333. [19] K. Bouzek, V. Jiricny, R. Kodym, J. Kristal, T. Bystron, Electrochim. Acta 55 (2010) [20] D.B. Baker, M.W. Verbrugge, J. Newman, J. Electroanal. Chem. 314 (1991) 23. [21] K.B. Oldham, J. Electroanal. Chem. 337 (1992) 91. [22] A. Amatore, B. Fosset, J. Bartelt, M.R. Deakin, R.M. Wightman, J. Electroanal. Chem. 256 (1988) 255. [23] K.B. Oldham, T.J. Cardwell, J.H. Santos, A.M. Bond, J. Electroanal. Chem. 430 (1997) 25. [24] A.M. Bond, M. Fleischmann, J. Robinson, J. Electroanal. Chem. 168 (1984)

23 [25] I. Montenegro, M.A. Queiros, J.L. Daschbach (Eds.), Microelectrodes: Theory and Applications, Kluwer, Dordrecht, [26] C. Lee, F. C. Anson, J. Electroanal. Chem. 323 (1992) 381. [27] K. Aoki, Electroanalysis, 5 (1993) 627. [28] J.C. Myland, K.B. Oldham, J. Electroanal. Chem., 347 (1993) 49. [29] M. Ciszkowska, Z. Stojek, J. Electroanal. Chem. 466 (1999) 129. [30] A. Jaworski, Z. Stojek, J.G. Osteryoung, J. Electroanal. Chem. 558 (2003) 141. [31] K. Aoki, A. Tokida, Electrochim. Acta, 45 (2000) [32] C.A. Paddon, M. Atobe, T. Fuchigami, P. He, P. Watts, S.J. Haswell, G.J. Pritchard, S.D. Bull, F. Marken, J. Appl. Electrochem. 36 (2006) 617. [33] K. Aoki, M. Morita, 0. Niwa, H. Tabei, J. Electroanal. Chem. 256 (1988) 269. [34] O. Niwa, M. Morita, H. Tabei, Anal. Chem. 62 (1990) 447. [35] V. A.T. Dam, W. Olthuis, A. van den Berg, Analyst, 132 (2007) 365. [36] S. Bose, T. Kuila, T.X.H. Nguyen, N.H. Kim, K.-t. Lau, J.H. Lee, Prog. Polym. Sci. 36 (2011) 813. [37] A. Goni-Urtiaga, D. Presvytes, K. Scott, Intern. J. Hydrog. Engy. 37 (2012) [38] J. Lu, D.-J. Li, L.-L. Zhang, Y.-X. Wang, Electrochim. Acta 53 (2007) 768. [39] D. Baker, M.W. Verbrugge, J. Newman, J. Electroanal. Chem. 314 (1991) 23. [40] B. Pillay, J. Newman, J. Electrochem. Soc. 140 (1993) 414. [41] P. Delahay, New Instrumental Methods in Electrochemistry, Interscience, New York, 1954, p